US4504318A - Process for producing plastic concrete - Google Patents

Process for producing plastic concrete Download PDF

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Publication number
US4504318A
US4504318A US06/547,393 US54739383A US4504318A US 4504318 A US4504318 A US 4504318A US 54739383 A US54739383 A US 54739383A US 4504318 A US4504318 A US 4504318A
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Prior art keywords
weight
parts
cement
polyalkylene glycol
inverted emulsion
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Expired - Lifetime
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US06/547,393
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Hideaki Matsuda
Takasi Saheki
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National House Industrial Co Ltd
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Okura Industrial Co Ltd
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Assigned to OKURA KOGYO KABUSHIKI KAISHA reassignment OKURA KOGYO KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MATSUDA, HIDEAKI, SAHEKI, TAKASI
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Assigned to NATIONAL HOUSE INDUSTRIAL CO., LTD. reassignment NATIONAL HOUSE INDUSTRIAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OKURA KOGYO KABUSHIKI KAISHA
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals

Definitions

  • This invention relates to a process for efficiently producing light-weight and high strength plastic concrete showing less shrinkage by forming a water-in-oil type emulsion of vinyl monomers and a cement slurry in the presence of a polyalkylene glycol derivative having terminal carboxyl groups, which is an addition product of polyalkylene glycol and a dibasic acid anhydride, and hardening and drying the emulsion.
  • cement concrete is widely used in the fields of civil engineering and construction industry at present but such a concrete has faults that it has heavy weight and is brittle.
  • it is required to introduce fine foams in cement slurry or intermixing light-weight aggregates with cement slurry but such an attempt is poor in practicability since the concrete shows large shrinkage by drying, creep, etc., as well as is inferior in strength.
  • a process is employed at present wherein cement concrete is cured under high-temperature and high-pressure saturated vapor.
  • the foregoing method is yet insufficient for obtaining high-strength concrete.
  • polymer-impregnated concrete As an attempt for greatly increasing the physical or mechanical strength of light-weight concrete, polymer-impregnated concrete is proposed. Such a concrete is prepared by impregnating a light-weight concrete base material with a vinyl monomer and polymerizing the vinyl monomer by the irradiation of radiation or by impregnating a light-weight concrete base material with a vinyl monomer having previously mixed with a polymerization initiator and polymerizing the vinyl monomer by heating.
  • the physical strength of the polymer-impregnated concrete obtained by the foregoing process is greatly improved as compared to the base material as well as the elastic property, chemical resistance, freezing and melting resistance, etc., of the concrete are also improved.
  • polymer-impregnated concrete has various problems in productivity.
  • vinyl monomers form a low-viscous water-in-oil type inverted emulsion in the presence of a polyalkylene glycol derivative having terminal carboxyl groups, which is an addition product of a polyalkylene glycol represented by the following general formula and a dibasic acid anhydride ##STR2## wherein R represents an alkyl group having one or more carbon atoms and a cement slurry, and further the inventors have succeeded in producing a light-weight high-strength plastic concrete at a high efficiency by polymerizing the foregoing inverted emulsion in the presence of a polymerization catalyst while hardening the cement and drying it.
  • the invention is a process of producing a plastic concrete which comprises forming a water-in-oil type inverted emulsion of vinylmonomers in the presence of a polyalkylene glycol derivative having terminal carboxyl groups, which is an addition product of the polyalkylene glycol shown by the foregoing general formula and a dibasic acid anhydride, and a cement slurry and polymerizing the inverted emulsion in the presence of a polymerization catalyst while hardening the cement.
  • the feature of this invention is in the point of discovering a novel process of producing a plastic concrete by utilizing a low-viscous water-in-oil type inverted emulsion, whereby the reduction of the weight of a cement concrete and the reinforcement of the concrete by the introduction of a polymer are simultaneously achieved.
  • FIG. 1 is a microscopic photograph of the light-weight plastic concrete of this invention obtained in Example 7.
  • the specific gravity of the plastic concrete obtained by the process of this invention can be desirably selected by controlling the amount of water added to the cement. That is, if the amount of water to cement is larger, the specific gravity of the plastic concrete obtained by drying the cured product is lower, while if the amount of water is smaller, the specific gravity is higher. Also, the water-in-oil type emulsion obtained in the process of this invention has a low viscosity as the feature thereof and can be easily mixed with organic or inorganic fillers and reinforcing agents. The plastic concrete thus obtained may be used as a water-containing hardened product without drying.
  • the inverted emulsion in this invention is produced by adding a cement slurry to vinyl monomers in the presence of the foregoing polyalkylene glycol derivative followed by vigorously stirring.
  • additives such as a reinforcing agent, a light-weight aggregate, a flame retardant agent, a filler, a coloring agent, etc., may be added to the mixture.
  • the polyalkylene glycol used for preparing the above-described polyalkylene glycol derivative is shown by the foregoing general formula and preferred examples of it are polypropylene glycol, polybutylene glycol, etc. It is proper that the mean molecular weight of the polyalkylene glycol is in a range of 1,000 to 10,000, preferably 2,000 to 5,000. If the mean molecular weight of the polyalkylene glycol is less than 1,000, the inverted emulsion is reluctant to form and if the mean molecular weight is larger than 10,000, the viscosity of the emulsion becomes too high, whereby making the treatment of the emulsion inconvenient.
  • dibasic acid anhydride there is no particular restriction about the dibasic acid anhydride to be added to the terminal hydroxy groups of the aforesaid polyalkylene glycol and examples of the dibasic acid anhydride are phthalic anhydride, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, etc., but in particular, maleic anhydride and succinic anhydride by which the addition reaction easily proceed are preferred.
  • the above-described polyalkylene glycol derivative has terminal carboxy groups bonded thereto by an ester bond and the terminal carboxy groups are neutralized by a metal cation such as Ca ++ , Mg ++ , etc., generated from a cement slurry in the step of mixing the cement slurry and vinyl monomers and vigorously stirring the mixture.
  • the neutralized product composed of the metal cation of the polyalkylene glycol derivative formed by the mechanism as described above act as effective water-in-oil type emulsifier for vinyl monomers, whereby a water-in-oil type inverted emulsion is formed.
  • the polyalkylene glycol derivative can be used as it is without need of previously neutralizing the polyalkylene glycol derivative with a basic material, etc., and hence a neutralization step becomes unnecessary, which is profitable in industrial production.
  • a neutralization reaction occurs in the step of adding a cement slurry to form an inverted emulsion.
  • vinyl monomer used for producing the foregoing inverted emulsion there is no particular restriction on a vinyl monomer used for producing the foregoing inverted emulsion and examples of the vinyl monomers are styrene, ⁇ -methylstyrene, acrylic acid esters, methacrylic acid esters, acrylonitrile, divinylbenzene, diacrylic acid esters or methacrylic acid esters of an alkylene glycol, acrylic acid esters or methacrylic acid esters of a polyhydric alcohol, etc. These monomers may be used solely or as a mixture of them.
  • the vinyl monomer for improving the heat resistance and other properties of the vinyl polymer formed, it is generally preferred to use the vinyl monomer together with a divinyl compound or a trivinyl compound such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc.
  • cement used for producing the cement slurry there is also no particular restriction on cement used for producing the cement slurry and there are Portland cement, blast furnace cement, fly ash cement, alumina cement, magnesia cement, etc.
  • the cement slurry is prepared by mixing well cement and water.
  • weight ratio there is no particular restriction on the weight ratio but it is preferred that the cement/water ratio be about 100/20 to about 100/500 by weight ratio.
  • the amount of the polyalkylene glycol derivative used for preparing the inverted emulsion is generally about 1 to 50 parts by weight, preferably about 3 to 30 parts by weight per 100 parts by weight of the vinyl monomer. If the amount of the polyalkylene glycol derivative is larger than 50 parts by weight, the viscosity of the inverted emulsion obtained becomes higher and the properties of the plastic concrete obtained by curing and hardening the inverted emulsion are not good. Also, if the amount of the polyalkylene glycol derivative is less than 1 part by weight, a stable inverted emulsion is not obtained.
  • the inverted emulsion can be cast even when the emulsion is mixed with organic or inorganic filler and/or reinforcing agent. This is one of the features of this invention and is very convenient in the case of producing casts.
  • the inverted emulsion prepared as described above is polymerized in the presence of a polymerization catalyst and in this case, a radical forming agent or a redox catalyst may be used as the polymerization catalyst.
  • a radical forming agent or a redox catalyst may be used as the polymerization catalyst.
  • cement is further hardened while polymerizing the vinyl monomer as described above and a hardening method employed for ordinary cement may be used for hardening the cement in this invention.
  • a hardening method employed for ordinary cement may be used for hardening the cement in this invention.
  • the cement may be cured in saturated water vapor or in water.
  • the water-containing plastic concrete obtained by polymerizing the vinyl monomers and hardening the cement by the manners as described above may be used as a water-containing hardened product without drying.
  • high specific gravity but high-strength plastic concrete can be obtained by producing an inverted emulsion while reducing the content of water in the step of producing a cement slurry as low as possible and then polymerizing and hardening the inverted emulsion.
  • crushed stone, sand, perlite, glass fibers, metal fibers, synthetic fibers, etc. in the inverted emulsion in the case of producing the emulsion, plastic concrete having various properties can be produced.
  • the inverted emulsion can be polymerized and hardened in a short period of time after pouring the emulsion in a mold, whereby the shortening of the time necessary for the completion of work in the fields of civil engineering and construction industry can be expected.
  • the water-containing plastic concrete may be dried to remove water therefrom.
  • the mixing ratio of cement and water in the case of producing a cement slurry by changing the mixing ratio of cement and water in the case of producing a cement slurry, light-weight plastic concretes having various specific gravities can be produced.
  • a light weight and a high strength are required, it is effective to increase the polymer content in the plastic concrete.
  • the physical strength of the plastic concrete can be also increased by incorporating glass fibers, metal fibers, synthetic fibers, etc., in the cement slurry.
  • light-weight plastic concrete having a high fire-retarding property can be produced by incorporating a flame retardant agent such as aluminium hydroxide, etc., in the cement slurry.
  • plastic concrete of this invention scarecely causes shrinkage by drying, large cast products can be produced.
  • the plastic concrete obtained by the process of this invention can be used for not only civil engineering and construction industry but also various uses such as casting materials, etc.
  • TMPT trimethylolpropane trimethacrylate
  • PPGMA-3,000 a maleic anhydride addition product of polypropylene glycol having a mean molecular weight of 3,000 (hereinafter, is referred to as PPGMA-3,000) was mixed 700 parts by weight of a slurry composed of 100 parts by weight of Portland cement, 200 parts by weight of river sand, and 400 parts by weight of water with stirring to provide a cement-containing inverted emulsion having good casting property.
  • the inverted emulsion was polymerized and cured by the same manner as in Example 1 and then dried to provide a light and tough plastic concrete.
  • methyl methacrylate 20 parts by weight of TMPT, and 8 parts by weight of PPGMA-3,000 was mixed 600 parts of a slurry composed of 200 parts by weight of Portland cement and 400 parts by weight of water with stirring to provide a cement-containing inverted emulsion having good casting property.
  • the inverted emulsion was polymerized and cured by the same manner as in Example 1 and dried to provide a light and tough plastic concrete.
  • a cement slurry obtained by mixing well 100 parts by weight of Portland cement, 360 parts by weight of river sand, and 72 parts by weight of water with stirring was poured into a mold and then withdrawn from the mold after 20 hours.
  • the product was cured for 7 days in a chamber maintained at a constant temperature of 40° C. and a constant humidity of 95% RH, and then dried to provide a concrete block.
  • a cement slurry obtained by mixing well 100 parts by weight of Portland cement, 109 parts by weight of perlite, and 273 parts by weight of water with stirring was treated by the same manner as in Comparison example 1 to provide a light-weight concrete block for measuring physical strength.
  • a cement slurry obtained by mixing well 100 parts by weight of Portland cement, 24 parts by weight of foamed polystyrene beads, and 40 parts by weight of water with stirring was treated by the same manner as in Comparison example 1 to provide a light-weight concrete block.
  • the light-weight plastic concretes obtained by the process of this invention generally have high physical strength and, in particular, the reinforcing effect of glass fibers on the bending strength is remarkable as shown in Examples 4 and 6.
  • the microscopic photograph of the light-weight plastic concrete obtained in Example 7 is shown in FIG. 1.
  • the diameters of foams in the concrete are very fine as about 10 ⁇ and the foams have uniform distribution of diameters. Since foams of the concrete are invisible, a light-weight plastic concrete having beautiful external surface state different from conventional light-weight concrete can be obtained.
  • PPGSA-3,000 a succinic anhydride addition product of polypropylene glycol having a mean molecular weight of 3,000
  • PPGSA-3,000 a succinic anhydride addition product of polypropylene glycol having a mean molecular weight of 3,000
  • Example 12 The same procedure as in Example 12 was followed except that calcium carbonate was used in place of Portland cement for producing an inverted emulsion but no inverted emulsion was formed.
  • Comparing Example 11 with Comparison example 6 shows that when other composition is same, the use of Portland cement clearly gives higher physical properties than the use of calcium carbonate. Also, the reason that the specific gravity of the light-weight plastic concrete using Portland cement became slightly higher is considered to be caused by the absorption of water at hardening the cement.
  • the concrete plate passed the test as a semi-noncombustible material.
  • TD ⁇ was generally high and the tendency of prolonging the residual flame time was observed.
  • the flame retarding property can be easily improved by adding thereto a flame retardant agent such as aluminium hydroxide, which is very convenient in the case of using the plastic concrete as an interior material requiring a flame retarding property.
  • a flame retardant agent such as aluminium hydroxide
  • the plastic concrete of this invention is a novel and useful material having a wide adaptability for various uses.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Polymerisation Methods In General (AREA)
US06/547,393 1983-01-20 1983-10-31 Process for producing plastic concrete Expired - Lifetime US4504318A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58-6685 1983-01-20
JP58006685A JPS59137354A (ja) 1983-01-20 1983-01-20 プラスチツクコンクリ−トの製造方法

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JP (1) JPS59137354A (enrdf_load_stackoverflow)
DE (1) DE3401813A1 (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4587279A (en) * 1984-08-31 1986-05-06 University Of Dayton Cementitious building material incorporating end-capped polyethylene glycol as a phase change material
US4614755A (en) * 1985-02-04 1986-09-30 Rodgers Jack L Protective coating composition comprising a blend of polyvinyl acetate, hydraulic cement, EVA, and limestone
DE3540155A1 (de) * 1985-09-03 1987-03-05 Hoerling Ludwig Chem Zusatzmittel fuer beton- und moertelmischungen und verfahren zu seiner herstellung
US4662942A (en) * 1983-08-01 1987-05-05 Idemitsu Petrochemical Co., Ltd. Cement additives
US5082878A (en) * 1988-04-15 1992-01-21 W.R. Grace & Co.-Conn Shrink controlled low-temperature-curable polyester resin compositions
US5108511A (en) * 1990-04-26 1992-04-28 W.R. Grace & Co.-Conn. Non-emulsion masonry cement additives and method of producing masonry cement compositions containing same
US5759260A (en) * 1993-07-16 1998-06-02 Rigro Inc. Method for using lightweight concrete for producing a combination therefrom and a combination produced thereby
US6030572A (en) * 1997-11-26 2000-02-29 Environmentally Engineered Concrete Products, Inc. Method for making a plastic aggregate
US6048916A (en) * 1996-04-03 2000-04-11 Nippon Shokubai Co., Ltd. Method for dispersion of cement
US7875231B1 (en) * 2007-02-26 2011-01-25 Bracegirdle Paul E Method for producing fiber reinforced cement-based structural building materials
US20120010324A1 (en) * 2010-07-09 2012-01-12 Halliburton Energy Services, Inc Hybrid Cement Set-On-Command Compositions
US8695705B2 (en) 2011-10-05 2014-04-15 Halliburton Energy Services, Inc. Composite formulations and methods of making and using same
US8770291B2 (en) 2010-07-09 2014-07-08 Halliburton Energy Services, Inc. Hybrid cement set-on-command compositions and methods of use
CN107949549A (zh) * 2015-07-20 2018-04-20 赢创德固赛有限公司 用于无机粘结剂的新型减缩剂

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61163156A (ja) * 1985-01-09 1986-07-23 大倉工業株式会社 プラスチツクコンクリ−トの製造法
JPS61186252A (ja) * 1985-02-12 1986-08-19 大倉工業株式会社 プラスチツクコンクリ−ト成型物の製造方法
US4734452A (en) * 1985-08-07 1988-03-29 Nippon Shokubai Kagaku Kogyo Co., Ltd. Curable composition, method for manufacturing thereof, and uses thereof
JPS62260745A (ja) * 1985-11-19 1987-11-13 チエン　チヨン　リン 水硬性材料、コンクリ−ト材料およびコンクリ−トの製造方法
DE3738602A1 (de) * 1987-11-13 1989-05-24 Cassella Ag Hydrophile quellbare pfropfpolymerisate, deren herstellung und verwendung
DE3920795C2 (de) * 1988-07-01 1999-06-24 Mbt Holding Ag Asymmetrische Diester, Verfahren zu deren Herstellung und diese enthaltende Zubereitungen
DE3910563A1 (de) * 1989-04-01 1990-10-04 Cassella Ag Hydrophile, quellfaehige pfropfcopolymerisate, deren herstellung und verwendung
DE3911433A1 (de) * 1989-04-07 1990-10-11 Cassella Ag Hydrophile quellfaehige pfropfpolymerisate, deren herstellung und verwendung
DE4207235A1 (de) * 1992-03-07 1993-09-09 Norbert Dipl Ing Lang Daemmaterial sowie verfahren zu seiner herstellung
DE4421722A1 (de) * 1994-06-21 1996-01-04 Sueddeutsche Kalkstickstoff Fließmittel für zementhaltige Bindemittelsuspensionen
DE10226176A1 (de) * 2002-06-12 2003-12-24 Basf Ag Bauelementen aus Leichtbeton, insbesondere für den Hochbau, sowie Verfahren zur Erhöhung der Druckfestigkeit eines Bauelements aus Leichtbeton
JP2006124231A (ja) * 2004-10-28 2006-05-18 Panahome Corp セメント系成形体

Citations (4)

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US3692728A (en) * 1971-03-08 1972-09-19 Progil Hydraulic binders and compositions including these binders
US3850651A (en) * 1972-04-13 1974-11-26 Ici Ltd Cementing compositions and concretes and mortars derived therefrom
US3950295A (en) * 1973-02-03 1976-04-13 Mitsui Toatsu Chemicals, Incorporated Method of preparing a composition containing gypsum, a vinyl monomer and sulfite ion
US4202809A (en) * 1977-07-15 1980-05-13 The Dow Chemical Company Styrene-butadiene-acrylonitrile interpolymer latex based cement additives

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AU515778B2 (en) * 1977-03-23 1981-04-30 Syncrete S.A. Method for forming a composition for use asa concrete substitute

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692728A (en) * 1971-03-08 1972-09-19 Progil Hydraulic binders and compositions including these binders
US3850651A (en) * 1972-04-13 1974-11-26 Ici Ltd Cementing compositions and concretes and mortars derived therefrom
US3950295A (en) * 1973-02-03 1976-04-13 Mitsui Toatsu Chemicals, Incorporated Method of preparing a composition containing gypsum, a vinyl monomer and sulfite ion
US4202809A (en) * 1977-07-15 1980-05-13 The Dow Chemical Company Styrene-butadiene-acrylonitrile interpolymer latex based cement additives

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4662942A (en) * 1983-08-01 1987-05-05 Idemitsu Petrochemical Co., Ltd. Cement additives
US4587279A (en) * 1984-08-31 1986-05-06 University Of Dayton Cementitious building material incorporating end-capped polyethylene glycol as a phase change material
US4614755A (en) * 1985-02-04 1986-09-30 Rodgers Jack L Protective coating composition comprising a blend of polyvinyl acetate, hydraulic cement, EVA, and limestone
DE3540155A1 (de) * 1985-09-03 1987-03-05 Hoerling Ludwig Chem Zusatzmittel fuer beton- und moertelmischungen und verfahren zu seiner herstellung
US5082878A (en) * 1988-04-15 1992-01-21 W.R. Grace & Co.-Conn Shrink controlled low-temperature-curable polyester resin compositions
US5108511A (en) * 1990-04-26 1992-04-28 W.R. Grace & Co.-Conn. Non-emulsion masonry cement additives and method of producing masonry cement compositions containing same
US5759260A (en) * 1993-07-16 1998-06-02 Rigro Inc. Method for using lightweight concrete for producing a combination therefrom and a combination produced thereby
US6048916A (en) * 1996-04-03 2000-04-11 Nippon Shokubai Co., Ltd. Method for dispersion of cement
US6030572A (en) * 1997-11-26 2000-02-29 Environmentally Engineered Concrete Products, Inc. Method for making a plastic aggregate
US7875231B1 (en) * 2007-02-26 2011-01-25 Bracegirdle Paul E Method for producing fiber reinforced cement-based structural building materials
US20120010324A1 (en) * 2010-07-09 2012-01-12 Halliburton Energy Services, Inc Hybrid Cement Set-On-Command Compositions
EP2591063A1 (en) * 2010-07-09 2013-05-15 Halliburton Energy Services, Inc. Hybrid cement set-on-command compositions
AU2011275527B2 (en) * 2010-07-09 2014-01-16 Halliburton Energy Services, Inc Hybrid cement set-on-command compositions
US8770291B2 (en) 2010-07-09 2014-07-08 Halliburton Energy Services, Inc. Hybrid cement set-on-command compositions and methods of use
US9441147B2 (en) * 2010-07-09 2016-09-13 Halliburton Energy Services, Inc. Hybrid cement set-on-command compositions
US8695705B2 (en) 2011-10-05 2014-04-15 Halliburton Energy Services, Inc. Composite formulations and methods of making and using same
CN107949549A (zh) * 2015-07-20 2018-04-20 赢创德固赛有限公司 用于无机粘结剂的新型减缩剂
US20180194682A1 (en) * 2015-07-20 2018-07-12 Frank Schubert Novel shrinkage-reducing agents for mineral binders
CN116986855A (zh) * 2015-07-20 2023-11-03 赢创运营有限公司 用于无机粘结剂的新型减缩剂
CN107949549B (zh) * 2015-07-20 2024-03-19 赢创运营有限公司 用于无机粘结剂的新型减缩剂

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Publication number Publication date
DE3401813A1 (de) 1984-07-26
DE3401813C2 (enrdf_load_stackoverflow) 1992-02-20
JPS64341B2 (enrdf_load_stackoverflow) 1989-01-06
JPS59137354A (ja) 1984-08-07

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